Non-surfactant solubilizing agent

ABSTRACT

Compositions of the invention include: (a) a solvent at least partially immiscible in water; and (b) a solubilizing agent having a formula:  
                 
 
     where R is (C 1 -C 7 )alkyl, substituted (C 1 -C 7 )alkyl, (C 1 -C 7 )alkoxy, substituted (C 1 -C 7 )alkoxy, (C 2 -C 7 )alkenyl, substituted (C 2 -C 7 )alkenyl, aryl, heteroaryl, cycloalkyl or heterocycly; and R′ and R″ is independently selected from hydrogen, (C 1 -C 7 )alkyl, substituted (C 1 -C 7 )alkyl, (C 1 -C 7 )alkoxy, substituted (C 1 -C 7 )alkoxy, (C 2 -C 7 )alkenyl, or substituted (C 2 -C 7 )alkenyl. Further compositions include: (a) a solvent at least partially immiscible in water; and (b) a solubilizing agent having a formula: 
     R 1 —R—OH 
     where R is (C 1 -C 7 )alkyl, substituted (C 1 -C 7 )alkyl, (C 1 -C 7 )alkoxy, substituted (C 1 -C 7 )alkoxy, (C 2 -C 7 )alkenyl, substituted (C 2 -C 7 )alkenyl, aryl, heteroaryl, cycloalkyl or heterocycyl and R 1  is a nitrogen containing heterocycyl or a nitrogen containing hetroaryl. The compositions are useful in providing stable single phase aqueous solutions when combined with water.

BACKGROUND OF THE INVENTION

[0001] The invention relates to cleaner/degreaser compositions and, moreparticularly, to stable cleaner/degreaser compositions that includesolvents with an HLB value between 5 and 7 made soluble in water with anon-surfactant solubilizing agent.

[0002] While not wishing to be held to any theory as to the nature ofthe cleaning and degreasing action of presently available compositions,it is believed that highly or infinitely water soluble organic solventspresently used in both retail as well as industrial and institutionalcleaner/degreaser compositions are too hydrophilic in nature to functioneffectively in removing hydrophobic “oleophilic” soilants, especially inthe presence of diluting water. As the level of the latter is increasedto bring conventional compositions to ready to use strength, thesolvating action of the organic solvent is drastically reduced with aconsequent and marked reduction in the cleaning/degreasing actionrequired for effective cleaning and oily soilant removal.

[0003] There remains a need, therefore, for cleaning, degreasercompositions with improved cleaning and degreasing capabilities wherethe solubilizing agent is a non surfactant solubilizing agent andwithout the other deficiencies of presently available cleaner/degreasercompositions.

DETAILED DESCRIPTION

[0004] Definitions

[0005] For the following defined terms, these definitions shall beapplied, unless a different definition is given in the claims orelsewhere in this specification.

[0006] All numeric values are herein assumed to be modified by the term“about,” whether or not explicitly indicated. The term “about” generallyrefers to a range of numbers that one of skill in the art would considerequivalent to the recited value (i.e., having the same function orresult). In many instances, the terms “about” may include numbers thatare rounded to the nearest significant figure.

[0007] Weight percent, percent by weight, % by weight, and the like aresynonyms that refer to the concentration of a substance as the weight ofthat substance divided by the weight of the composition and multipliedby 100.

[0008] The recitation of numerical ranges by endpoints includes allnumbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2,2.75, 3, 3.80, 4, and 5).

[0009] As used in this specification and the appended claims, thesingular forms “a”, “an”, and “the” include plural referents unless thecontent clearly dictates otherwise. Thus, for example, reference to acomposition containing “a compound” includes a mixture of two or morecompounds. As used in this specification and the appended claims, theterm “or” is generally employed in its sense including “and/or” unlessthe content clearly dictates otherwise.

[0010] The term “alkyl” refers to a straight or branched chainmonovalent hydrocarbon radical having a specified number of carbonatoms. Alkyl groups may be unsubstituted or substituted withsubstituents that do not interfere with the specified function of thecomposition and may be substituted once or twice with the same ordifferent group. Substituents may include alkoxy, hydroxy, mercapto,amino, alkyl substituted amino, nitro, carboxy, carbanoyl, carbanoyloxy,cyano, methylsulfonylamino, or halo, for example. Examples of “alkyl”include, but are not limited to, methyl, ethyl, n-propyl, isopropyl,n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, 3-methylpentyl, and thelike.

[0011] The term “alkoxy” refers to refers to a straight or branchedchain monovalent hydrocarbon radical having a specified number of carbonatoms and a carbon-oxygen-carbon bond, may be unsubstituted orsubstituted with substituents that do not interfere with the specifiedfunction of the composition and may be substituted once or twice withthe same or different group. Substituents may include alkoxy, hydroxy,mercapto, amino, alkyl substituted amino, nitro, carboxy, carbanoyl,carbanoyloxy, cyano, methylsulfonylamino, or halo, for example. Examplesinclude, methoxy, ethoxy, propoxy, t-butoxy, and the like.

[0012] The term “alkenyl” or “alkenylene” refers to a straight orbranched chain divalent hydrocarbon radical having a specified number ofcarbon atoms and one or more carbon--carbon double bonds. Alkenylenegroups may be unsubstituted or substituted with substituents that do notinterfere with the specified function of the composition and may besubstituted once or twice with the same or different group. Substituentsmay include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino,nitro, carboxy, carbanoyl, carbanoyloxy, cyano, methylsulfonylamino, orhalo, for example. Examples of “alkenyl” or “alkenylene” include, butare not limited to, ethene-1,2-diyl, propene-1,3-diyl, and the like.

[0013] The term “cycloalkyl” refers to an alicyclic hydrocarbon grouphaving a specified number of carbon atoms. Cycloalkyl groups includethose with one to twelve carbon atoms. Cycloalkyl groups may besaturated or unsaturated, unsubstituted or substituted with thosesubstituents that do not interfere with the specified function of thecomposition. Cycloalkyl may be substituted by halo, C₁-C₆ alkyl, C₁-C₆alkoxy, C₂-C₆ alkenyl, substituted C₁-C₆ alkyl, C₁-C₆ substitutedalkoxy, substituted C₂-C₆ alkenyl, substituted alkoxy, amino, nitro,cyano, carboxy, hydroxymethyl, aminomethyl, carboxymethyl, C₁-C₄alkylthio, hydroxy, C₁-C₄ alkanoyloxy, carbamoyl, or halo-substitutedC₁-C₆ alkyl and may be substituted once or more with the same ordifferent group. Such a cycloalkyl ring may be optionally fused to oneor more of another heteroaryl ring(s), aryl ring(s), or cycloalkylrings. Examples of “cycloalkyl” include, but are not limited to,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, orcyclooctyl, and the like.

[0014] The term “heterocyclic” or “heterocyclyl” refers to a monovalentthree to twelve-membered non-aromatic ring containing one or moreheteroatomic substitutions independently selected from S, O, or N andhaving zero to five degrees of unsaturation. Heterocyclyl groups may beunsubstituted or substituted with those substituents that do notinterfere with the specified function of the composition. Heterocyclylmay be substituted by halo, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₂-C₆ alkenyl,substituted C₁-C₆ alkyl, C₁-C₆ substituted alkoxy, substituted C₂-C₆alkenyl, substituted alkoxy, amino, nitro, cyano, carboxy,hydroxymethyl, aminomethyl, carboxymethyl, C₁-C₄ alkylthio, hydroxy,C₁-C₄ alkanoyloxy, carbamoyl, or halo-substituted C₁-C₆ alkyl and may besubstituted once or more with the same or different group. Such aheterocyclic ring may be optionally fused to one or more of anotherheterocyclic ring(s), heteroaryl ring(s), aryl ring(s), or cycloalkylrings. Examples of “heterocyclic” include, but are not limited to,tetrahydrofuryl, pyranyl, 1,4-dioxanyl, 1,3-dioxanyl, piperidinyl,pyrrolidinyl, morpholinyl, tetrahydrothiopyranyl, tetrahydrothiophenyl,and the like.

[0015] The term “aryl” refers to monovalent unsaturated aromaticcarbocyclic radicals having a single ring, such as phenyl, or multiplecondensed rings, such as naphthyl or anthryl. Aryl groups may beunsubstituted or substituted with those substituents that do notinterfere with the specified function of the composition. Aryl may besubstituted by halo, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₂-C₆ alkenyl,substituted C₁-C₆ alkyl, C₁-C₆ substituted alkoxy, substituted C₂-C₆alkenyl, substituted alkoxy, amino, nitro, cyano, carboxy,hydroxymethyl, aminomethyl, carboxymethyl, C₁-C₄ alkylthio, hydroxy,C₁-C₄ alkanoyloxy, carbamoyl, or halo-substituted C₁-C₆ alkyl and may besubstituted once or more with the same or different group. Such an arylring may be optionally fused to one or more of another heterocyclicring(s), heteroaryl ring(s), aryl ring(s), or cycloalkyl rings. Examplesof “aryl” include, but are not limited to, phenyl, 2-naphthyl,1-naphthyl, biphenyl, 2-hydroxyphenyl, 2-aminophenyl, 2-methoxyphenyland the like.

[0016] The term “heteroaryl” refers to a monovalent five to sevenmembered aromatic ring radical containing one or more heteroatomsindependently selected from S, O, or N. Heteroaryl groups may beunsubstituted or substituted with those substituents that do notinterfere with the specified function of the composition. Heteroaryl maybe substituted by halo, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₂-C₆ alkenyl,substituted C₁-C₆ alkyl, C₁-C₆ substituted alkoxy, substituted C₂-C₆alkenyl, substituted alkoxy, amino, nitro, cyano, carboxy,hydroxymethyl, aminomethyl, carboxymethyl, C₁-C₄ alkylthio, hydroxy,C₁-C₄ alkanoyloxy, carbamoyl, or halo-substituted C₁-C₆ alkyl and may besubstituted once or more with the same or different group. Such a“heteroaryl” ring may be optionally fused to one or more of anotherheterocyclic ring(s), heteroaryl ring(s), aryl ring(s), or cycloalkylrings. Examples of “heteroaryl” include, but are not limited to, furyl,thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl,thiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl,isothiazolyl, pyridinyl, pyridazinyl, pyrazinyl, pyrimidinyl,quinolinyl, isoquinolinyl, benzofuryl, benzothiophenyl, indolyl, andindazolyl, and the like.

[0017] The term “halo” and “halogen” refer to chloro, bromo, fluoro, andiodo.

[0018] Compositions

[0019] The compositions of the invention include: (a) a solvent at leastpartially immiscible in water; and (b) a solubilizing agent having aformula:

[0020] where R is (C₁-C₇)alkyl, substituted (C₁-C₇)alkyl, (C₁-C₇)alkoxy,substituted (C₁-C₇)alkoxy, (C₂-C₇)alkenyl, substituted (C₂-C₇)alkenyl,aryl, heteroaryl, cycloalkyl or heterocycly; and R′ and R″ isindependently selected from hydrogen, (C₁-C₇)alkyl, substituted(C₁-C₇)alkyl, (C₁-C₇)alkoxy, substituted (C₁-C₇)alkoxy, (C₂-C₇)alkenyl,or substituted (C₂-C₇)alkenyl. When the solubilizing agent ismonoisopropanolamine the monoisopropanolamine is present in an amounteffective to form a stable single phase solution of solvent, water andmonoisopropanolamine.

[0021] Further compositions include: (a) a solvent at least partiallyimmiscible in water; and (b) a solubilizing agent having a formula:

R₁—R—OH

[0022] where R is (C₁-C₇)alkyl, substituted (C₁-C₇)alkyl, (C₁-C₇)alkoxy,substituted (C₁-C₇)alkoxy, (C₂-C₇)alkenyl, substituted (C₂-C₇)alkenyl,aryl, heteroaryl, cycloalkyl or heterocycyl and R₁ is a nitrogencontaining heterocycyl or a nitrogen containing hetroaryl.

[0023] Solvent

[0024] The solvent may be immiscible or insoluble in aqueous solutions.One measure of insolubility is known as hydrophilic-lipophilic balance(HLB). The hydrophilic-lipophilic balance scale is described by DowChemical Company at www.dow.com technical brochure entitled “Solvent HLBand OHLB Values for Dowanol Oxygenated solvents”, that is incorporatedby reference herein. While HLB is discussed herein, the non-surfactantcoupling agent will increase the solubility of any solvent that isimmiscible or partly insoluble in an aqueous solution at a giventemperature regardless of HLB value if any.

[0025] The solvent may have a hydrophilic-lipophilic balance (HLB) valueof 5 to 7. HLB is generally useful for predicting a solvent's solubilityin water. An HLB value less than 7 indicates that the solvent isgenerally hydrophobic. The HLB scale was derived initially forsurfactants and provides a means for comparing the relativehydrophilicity of amphiphilic molecules. HLB values are also relevantfor solvents, such as glycol ethers and the like. Substantially completewater solubility occurs at an HLB of around 7. Solvents with HLB valuesabove this mark are generally completely miscible in water, while thosebelow this value are generally only partially soluble in water. The HLBscale is useful for visualizing the ease of compatiblizing solvents intowater.

[0026] Solvents with a HLB value of 5 to 7 include, for example,propylene glycol phenyl ether (i.e., 1-phenoxy-2-propanol), tripropyleneglycol n-butyl ether (i.e.,(2-(2-butoxymethylethoxy)methylethoxy)-propanol), dipropylene glycoln-butyl ether (i.e., 1-(2-butoxy-1-methylethoxy)-2-propanol), propyleneglycol n-butyl ether (i.e., 1-butoxy-2-propanol), dipropylene glycoldimethyl ether (i.e., oxybis (methory)-propane), dipropylene glycoln-propyl ether (i.e., 1-(1-methyl-2-proproxyethyoxy)-2-propanol, ortripropylene glycol n-propyl ether (i.e., 1-(1 or3-methyl-2-(methyl(-2-propoxyethoxy) ethoxyl-propanol), and the like.These listed solvents are commercially available under the Dowanoltradename from Dow Chemical Company. Additional solvents that are atleast partly immiscible in water include, for example, benzyl alcohol,2-phenoxyethanol, and the like. These solvents are commerciallyavailable from Aldrich Chemical Company.

[0027] Solvents with an HLB value of greater than 7 may be included inthe compositions of the invention. Solvents with an HLB value of greaterthan 7, include, for example, propylene glycol methyl ether, dipropyleneglycol methyl ether, tripropylene glycol methyl ether, and the like.These listed solvents are commercially available under the Dowanoltradename from Dow Chemical Company.

[0028] As will be apparent to those skilled in the art, the above-listedsolvents are merely illustrative and various other solvents meeting thecriteria set out above may also be used in the practice of theinvention.

[0029] The solvent may be present in the composition from 0.01 wt % or 1to 99 wt % or 5 to 50 wt % based on the total weight of solvent, waterand solubilizing agent.

[0030] Solubilizing Agent

[0031] The solubilizing agent is a substance that increases thesolubility in water of another material that is only partially watersoluble, such as the solvents listed above. The solubilizing agent ofthe invention is a non-surfactant alcohol amine. The alcohol amine maybe a primary, secondary or ternary amine. The solubilizing agent mayhave the formula:

[0032] where R is (C₁-C₇)alkyl, substituted (C₁-C₇)alkyl, (C₁-C₇)alkoxy,substituted (C₁-C₇)alkoxy, (C₂-C₇)alkenyl, substituted (C₂-C₇)alkenyl,aryl, heteroaryl, cycloalkyl or heterocycly; and R′ and R″ areindependently selected from hydrogen, (C₁-C₇)alkyl, substituted(C₁-C₇)alkyl, (C₁-C₇)alkoxy, substituted (C₁-C₇)alkoxy, (C₂-C₇)alkenyl,or substituted (C₂-C₇)alkenyl. R may be (C₂-C₄) alkyl and R′ may behydrogen or C₂ alkyl. R may be (C₂-C₄)alkyl, R′ and R″ may be hydrogenor C₂ alkyl. When the solubilizing agent is monoisopropanolamine themonoisopropanolamine is present in an amount effective to form a stablesingle phase solution of solvent, water and monoisopropanolamine.Alternately, monoisopropanolamine can be excluded as the solubilizingagent or when R is isopropyl and R′ is hydrogen, then R″ is(C₁-C₇)alkyl, substituted (C₁-C₇)alkyl, (C₁-C₇)alkoxy, substituted(C₁-C₇)alkoxy, (C₂-C₇)alkenyl, or substituted (C₂-C₇)alkenyl. Thesolubilizing agent may be 2-amino-2-methyl-1-propanol, triethanolamine,diethanolamine, monoethanolamine, 5-aminopentanol or mixtures thereof.

[0033] The solubilizing agent may have the formula:

R₁—R—OH

[0034] where R is (C₁-C₇)alkyl, substituted (C₁-C₇)alkyl, (C₁-C₇)alkoxy,substituted (C₁-C₇)alkoxy, (C₂-C₇)alkenyl, substituted (C₂-C₇)alkenyl,aryl, heteroaryl, cycloalkyl or heterocycyl and R₁ is a nitrogencontaining heterocycyl or a nitrogen containing hetroaryl. R may be(C₁-C₄) alkyl and R₁ may be nitrogen containing heterocycyl. Thesolubilizing agent may be 1-piperidine ethanol.

[0035] Nitrogen containing heterocycles/heteroaryls include but are notlimited to, pyrrole, imidazole, pyrazole, pyridine, pyrazine,pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine,quinolizine, isoquinoline, quinoline, phthalazine, naphthylpyridine,quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline,phenanthridine, acridine, phenanthroline, isothiazole, phenazine,isoxazole, phenoxazine, phenothiazine, imidazolidine, imidazoline,piperidine, piperazine, indoline, morpholino, piperidinyl,tetrahydrofuranyl, and the like as well as N-alkoxy-nitrogen containingheterocycles.

[0036] Examples of non-surfactant alcohol amines include the followingnon-limiting structures:

[0037] The non-surfactant alcohol amine may be present in thecomposition from 0.01 wt % or 0.1 to 40 wt % or 15 to 35 wt % or 20 to25 wt % based on the total weight of solvent, water and solubilizingagent. If the non-surfactant alcohol amine is monoisopropanolamine, thenthe monoisopropanolamine may be present in an amount in excess of 10 wt% or from 10 to 40 wt % or from 20 to 25 wt %.

[0038] Water

[0039] The compositions of the invention may include water. Thesolubilizing agent can be present in the composition in an amounteffective to increase the solubility of the solvent that is at leastpartially insoluble in water or having an HBL value of 5 to 7 in water.Enough solubilizing agent can be present in the composition to allow thesolvent having an HBL value of 5 to 7 to be completely miscible in thewater present.

[0040] Water may be present in the composition from 0.01% wt or 1 to 99wt % or 25 to 75 wt % based on the total weight of solvent, water andsolubilizing agent.

[0041] The composition may include any amount of solvent, solubilizingagent or water. The compositions may include 1-99% wt solvent, 1-99% wtwater and 0.1-40% wt solubilizing agent based on total weight ofsolvent, water and solubilizing agent in the composition. Thecompositions may include 5-50% wt solvent, 25-75% wt water and 15-35% wtsolubilizing agent based on total weight of solvent, water andsolubilizing agent in the composition. The compositions may include5-50% wt solvent, 25-75% wt water and 20-25% wt solubilizing agent basedon total weight of solvent, water and solubilizing agent in thecomposition.

[0042] The compositions may include enzymes, enzyme stabilizing system,surfactant, chelating agents, sequestering agents, bleaching agents,alkaline source, secondary hardening agent or solubility modifier,detergent filler, defoamer, anti-redeposition agent, a threshold agentor system, aesthetic enhancing agent (i.e. dye, perfume, ect.) and thelike. Adjuvants and other additive ingredients will vary according tothe type of composition being manufactured and can be included in thecompositions in any amount.

[0043] Enzymes

[0044] The composition of the invention may includes one or moreenzymes, which can provide desirable activity for removal ofprotein-based, carbohydrate-based, or triglyceride-based stains fromsubstrates; for cleaning, destaining, and sanitizing presoaks, such aspresoaks for flatware, cups and bowls, and pots and pans; presoaks formedical and dental instruments; or presoaks for meat cutting equipment;for machine warewashing; for laundry and textile cleaning anddestaining; for carpet cleaning and destaining; for cleaning-in-placeand destaining-in-place; for cleaning and destaining food processingsurfaces and equipment; for drain cleaning; presoaks for cleaning; andthe like. Enzymes may act by degrading or altering one or more types ofsoil residues encountered on a surface or textile thus removing the soilor making the soil more removable by a surfactant or other component ofthe cleaning composition. Both degradation and alteration of soilresidues can improve detergency by reducing the physicochemical forceswhich bind the soil to the surface or textile being cleaned, i.e. thesoil becomes more water soluble. For example, one or more proteases cancleave complex, macromolecular protein structures present in soilresidues into simpler short chain molecules which are, of themselves,more readily desorbed from surfaces, solubilized or otherwise moreeasily removed by detersive solutions containing said proteases.

[0045] Suitable enzymes may include a protease, an amylase, a lipase, agluconase, a cellulase, a peroxidase, or a mixture thereof of anysuitable origin, such as vegetable, animal, bacterial, fungal or yeastorigin. Selections are influenced by factors such as pH-activity and/orstability optima, thermostability, and stability to active detergents,builders and the like. In this respect bacterial or fungal enzymes maybe preferred, such as bacterial amylases and proteases, and fungalcellulases. Preferably the enzyme may be a protease, a lipase, anamylase, or a combination thereof. Enzyme may be present in thecomposition from at least 0.01 wt %, or 0.01 to 2 wt %.

[0046] Enzyme Stabilizing System

[0047] The composition of the invention may include an enzymestabilizing system. The enzyme stabilizing system can include a boricacid salt, such as an alkali metal borate or amine (e. g. analkanolamine) borate, or an alkali metal borate, or potassium borate.The enzyme stabilizing system can also include other ingredients tostabilize certain enzymes or to enhance or maintain the effect of theboric acid salt.

[0048] For example, the cleaning composition of the invention caninclude a water soluble source of calcium and/or magnesium ions. Calciumions are generally more effective than magnesium ions and are preferredherein if only one type of cation is being used. Cleaning and/orstabilized enzyme cleaning compositions, especially liquids, may include1 to 30, 2 to 20, or 8 to 12 millimoles of calcium ion per liter offinished composition, though variation is possible depending on factorsincluding the multiplicity, type and levels of enzymes incorporated.Water-soluble calcium or magnesium salts may be employed, including forexample calcium chloride, calcium hydroxide, calcium formate, calciummalate, calcium maleate, calcium hydroxide and calcium acetate; moregenerally, calcium sulfate or magnesium salts corresponding to thelisted calcium salts may be used. Further increased levels of calciumand/or magnesium may of course be useful, for example for promoting thegrease-cutting action of certain types of surfactant.

[0049] Stabilizing systems of certain cleaning compositions, for examplewarewashing stabilized enzyme cleaning compositions, may further include0 to 10%, or 0.01% to 6% by weight, of chlorine bleach scavengers, addedto prevent chlorine bleach species present in many water supplies fromattacking and inactivating the enzymes, especially under alkalineconditions. While chlorine levels in water may be small, typically inthe range from about 0.5 ppm to about 1.75 ppm, the available chlorinein the total volume of water that comes in contact with the enzyme, forexample during warewashing, can be relatively large; accordingly, enzymestability to chlorine in-use can be problematic.

[0050] Suitable chlorine scavenger anions are known and readilyavailable, and, if used, can be salts containing ammonium cations withsulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidantssuch as carbamate, ascorbate, etc., organic amines such asethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,monoethanolamine (MEA), and mixtures thereof can likewise be used.

[0051] Surfactant

[0052] A surfactant may be present in the composition of the invention.The surfactant or surfactant admixture can be selected from watersoluble or water dispersible nonionic, semi-polar nonionic, anionic,cationic, amphoteric, or zwitterionic surface-active agents; or anycombination thereof. The particular surfactant or surfactant mixturechosen for use in the process and products of this invention can dependon the conditions of final utility, including method of manufacture,physical product form, use pH, use temperature, foam control, and soiltype. For a discussion of surfactants, see Kirk-Othmer, Encyclopedia ofChemical Technology, Third Edition, volume 8, pages 900-912. Thecomposition may include a surfactant in an amount effective to provide adesired level of cleaning, such as 0-20 wt %, or 1.5-15 wt %.

[0053] Anionic surfactants may include, for example, carboxylates suchas alkylcarboxylates (carboxylic acid salts) and polyalkoxycarboxylates,alcohol ethoxylate carboxylates, nonylphenol ethoxylate carboxylates,and the like; sulfonates such as alkylsulfonates,alkylbenzenesulfonates, alkylarylsulfonates, sulfonated fatty acidesters, and the like; sulfates such as sulfated alcohols, sulfatedalcohol ethoxylates, sulfated alkylphenols, alkylsulfates,sulfosuccinates, alkylether sulfates, and the like; and phosphate esterssuch as alkylphosphate esters, and the like.

[0054] Nonionic surfactants may include those having a polyalkyleneoxide polymer as a portion of the surfactant molecule. Such nonionicsurfactants include, for example, chlorine-, benzyl-, methyl-, ethyl-,propyl-, butyl- and other like alkyl-capped polyethylene glycol ethersof fatty alcohols; polyalkylene oxide free nonionics such as alkylpolyglycosides; sorbitan and sucrose esters and their ethoxylates;alkoxylated ethylene diamine; alcohol alkoxylates such as alcoholethoxylate propoxylates, alcohol propoxylates, alcohol propoxylateethoxylate propoxylates, alcohol ethoxylate butoxylates, and the like;nonylphenol ethoxylate, polyoxyethylene glycol ethers and the like;carboxylic acid esters such as glycerol esters, polyoxyethylene esters,ethoxylated and glycol esters of fatty acids, and the like; carboxylicamides such as diethanolamine condensates, monoalkanolamine condensates,polyoxyethylene fatty acid amides, and the like; and polyalkylene oxideblock copolymers including an ethylene oxide/propylene oxide blockcopolymer such as those commercially available under the trademarkPLURONIC™ (BASF-Wyandotte), and the like; and other like nonioniccompounds. Silicone surfactants such as the ABIL™ B8852 can also beused.

[0055] Cationic surfactants useful for inclusion in a cleaningcomposition for sanitizing or fabric softening, include amines such asprimary, secondary and tertiary monoamines with C₁₈ alkyl or alkenylchains, ethoxylated alkylamines, alkoxylates of ethylenediamine,imidazoles such as a 1-(2-hydroxyethyl)-2-imidazoline, a2-alkyl-1-(2-hydroxyethyl)-2-imidazoline, and the like; and quaternaryammonium salts, as for example, alkylquatemary ammonium chloridesurfactants such as n-alkyl(C₁₂-C₁₈)dimethylbenzyl ammonium chloride,n-tetradecyl dimethylbenzylammonium chloride monohydrate, anaphthylene-substituted quaternary ammonium chloride such asdimethyl-1-naphthylmethylammonium chloride, and the like; and other likecationic surfactants.

[0056] Chelating/Sequestering Agent

[0057] The composition may include a chelating/sequestering agent suchas an aminocarboxylic acid, a condensed phosphate, a phosphonate, apolyacrylate, and the like. In general, a chelating agent is a moleculecapable of coordinating (i.e., binding) the metal ions commonly found innatural water to prevent the metal ions from interfering with the actionof the other detersive ingredients of a cleaning composition. Thechelating/sequestering agent may also function as a threshold agent whenincluded in an effective amount. The composition may include 0.1-70 wt%, or 5-60 wt %, of a chelating/sequestering agent. An iminodisuccinate(available commercially from Bayer as IDS™) may be used as a chelatingagent.

[0058] Useful aminocarboxylic acids include, for example,N-hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA),ethylenediaminetetraacetic acid (EDTA),N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA),diethylenetriaminepentaacetic acid (DTPA), and the like.

[0059] Examples of condensed phosphates useful in the presentcomposition include sodium and potassium orthophosphate, sodium andpotassium pyrophosphate, sodium tripolyphosphate, sodiumhexametaphosphate, and the like.

[0060] The composition may include a phosphonate such as1-hydroxyethane-1,1-diphosphonic acid and the like.

[0061] Polymeric polycarboxylates may also be included in thecomposition. Those suitable for use as cleaning agents have pendantcarboxylate groups and include, for example, polyacrylic acid,maleic/olefin copolymer, acrylic/maleic copolymer, polymethacrylic acid,acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide,hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamidecopolymers, hydrolyzed polyacrylonitrile, hydrolyzedpolymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrilecopolymers, and the like. For a further discussion of chelatingagents/sequestrants, see Kirk-Othmer, Encyclopedia of ChemicalTechnology, Third Edition, volume 5, pages 339-366 and volume 23, pages319-320, the disclosure of which is incorporated by reference herein.

[0062] Bleaching Agents

[0063] Bleaching agents for lightening or whitening a substrate, includebleaching compounds capable of liberating an active halogen species,such as Cl₂, Br₂, —OCl⁻ and/or —OBr⁻, under conditions typicallyencountered during the cleansing process. Suitable bleaching agentsinclude, for example, chlorine-containing compounds such as a chlorine,a hypochlorite, chloramine. Halogen-releasing compounds may include thealkali metal dichloroisocyanurates, chlorinated trisodium phosphate, thealkali metal hypochlorites, monochloramine and dichloramine, and thelike. Encapsulated chlorine sources may also be used to enhance thestability of the chlorine source in the composition (see, for example,U.S. Pat. Nos. 4,618,914 and 4,830,773, the disclosure of which isincorporated by reference herein). A bleaching agent may also be aperoxygen or active oxygen source such as hydrogen peroxide, perborates,sodium carbonate peroxyhydrate, phosphate peroxyhydrates, potassiumpermonosulfate, and sodium perborate mono and tetrahydrate, with andwithout activators such as tetraacetylethylene diamine, and the like. Acleaning composition may include a minor but effective amount of ableaching agent, such as 0.1-10 wt %, or 1-6 wt %.

[0064] Detergent Builders or Fillers

[0065] A composition may include a minor but effective amount of one ormore of a detergent filler which does not perform as a cleaning agentper se, but cooperates with the cleaning agent to enhance the overallcleaning capacity of the composition. Examples of fillers suitable foruse in the present cleaning compositions include sodium sulfate, sodiumchloride, starch, sugars, C₁-C₁₀ alkylene glycols such as propyleneglycol, and the like. Inorganic or phosphate-containing detergentbuilders may include alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (e.g. tripolyphosphates, pyrophosphates, and glassypolymeric meta-phosphates). Non-phosphate builders may also be used. Adetergent filler may be included in an amount of 1-20 wt %, or 3-15 wt%.

[0066] Defoaming Agents

[0067] A minor but effective amount of a defoaming agent for reducingthe stability of foam may also be included in the compositions. Thecleaning composition can include 0.01-5 wt % of a defoaming agent, or0.01-3 wt %.

[0068] Examples of defoaming agents include silicone compounds such assilica dispersed in polydimethylsiloxane, fatty amides, hydrocarbonwaxes, fatty acids, fatty esters, fatty alcohols, fatty acid soaps,ethoxylates, mineral oils, polyethylene glycol esters, alkyl phosphateesters such as monostearyl phosphate, and the like. A discussion ofdefoaming agents may be found, for example, in U.S. Pat. No. 3,048,548to Martin et al., U.S. Pat. No. 3,334,147 to Brunelle et al., and U.S.Pat. No. 3,442,242 to Rue et al., the disclosures of which areincorporated by reference herein.

[0069] Anti-Redeposition Agents

[0070] The composition may include an anti-redeposition agent capable offacilitating sustained suspension of soils in a cleaning solution andpreventing the removed soils from being redeposited onto the substratebeing cleaned. Examples of suitable anti-redeposition agents includefatty acid amides, fluorocarbon surfactants, complex phosphate esters,styrene maleic anhydride copolymers, and cellulosic derivatives such ashydroxyethyl cellulose, hydroxypropyl cellulose, and the like. Thecomposition may include 0.5-10 wt %, or 1-5 wt %, of ananti-redeposition agent.

[0071] Dyes/Odorants

[0072] Various dyes, odorants including perfumes, and other aestheticenhancing agents may also be included in the composition. Dyes may beincluded to alter the appearance of the composition, as for example,Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), AcidOrange 7 (American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23(GAF), Acid Yellow 17 (Sigma Chemical), Sap Green (Keyston Analine andChemical), Metanil Yellow (Keystone Analine and Chemical), Acid Blue 9(Hilton Davis), Sandolan Blue/Acid Blue 182 (Sandoz), Hisol Fast Red(Capitol Color and Chemical), Fluorescein (Capitol Color and Chemical),Acid Green 25 (Ciba-Geigy), and the like.

[0073] Fragrances or perfumes that may be included in the compositionsinclude, for example, terpenoids such as citronellol, aldehydes such asamyl cinnamaldehyde, a jasmine such as C1S-jasmine or jasmal, vanillin,and the like.

[0074] Alkalinity Source

[0075] An alkalinity source may be provided to increase the pH ofcomposition. Exemplary alkalinity sources include an alkali metalsilicate, hydroxide, phosphate, or carbonate.

[0076] The alkalinity source can include an alkali metal hydroxideincluding sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.Mixtures of these hydroxide species can also be used. Alkaline metalsilicates can also act as a source of alkalinity for the detergents ofthe invention.

[0077] The alkalinity source can include an alkali metal carbonate.Alkali metal carbonates which may be used include sodium carbonate,potassium carbonate, sodium or potassium bicarbonate or sesquicarbonate,among others. These sources of alkalinity can be used the compositionsof the invention at concentrations of 0.1 wt-% to 70 wt-%, 1 wt-% to 30wt-%, or 5 wt-% to 20 wt-%.

[0078] Divalent Ion

[0079] The compositions of the invention may contain a divalent ion,selected from calcium and magnesium ions, at a level of from 0.05% to 5%by weight, or from 0.1% to 1% by weight, or 0.25% by weight of thecomposition. The divalent ion can be, for example, calcium or magnesium.The calcium ions can, for example, be added as a chloride, hydroxide,oxide, formate, acetate, nitrate salt.

[0080] Polyol

[0081] The composition of the invention can also include a polyol. Thepolyol may provide additional stability and hydrotrophic properties tothe composition. Propylene glycol and sorbitol are preferred polyols.

[0082] The compositions of the invention may also contain additionaltypically nonactive materials, with respect to cleaning properties,generally found in liquid pretreatment or detergent compositions inconventional usages. These ingredients are selected to be compatiblewith the materials of the invention and include such materials as fabricsofteners, optical brighteners, soil suspension agents, germicides,viscosity modifiers, inorganic carriers, solidifying agents and thelike.

[0083] The above compositions can be made by combining water with asolvent having a HLB value of 5 to 7 and a solubilizing agent definedabove to form a stable single phase solution. The above processes can beused to produce a product having a stable single solution phase. Thecompositions can be diluted with aqueous and/or non aqueous materials toform a use solution of any strength depending on the application. Thecompositions of the invention may be in the form of a solid, liquid,gel, paste, structured liquid, and the like. The compositions anddiluted use solutions may be useful as, for example, detergents forlaundry, warewashing, vehicle care, sanitizing, ect.

EXAMPLES

[0084] Formulations were created by combining the components in theamounts listed in the tables below. A base composition consisted ofwater and solvents having an HLB value of a 5-7 shown in Table 1 below:TABLE 1 Component Wt % Water 55 Diproplyene Glycol n-Butyl Ether 20(Dowanol DPnB ™) Benzyl Alcohol 15 Propylene Glycol Phenyl Ether 10

[0085] Several non-surfactant solubilizing agent were obtained fromAldrich Chemical Company and added to the base composition to determineif they where able to solubilize solvents having an HLB value of 5-7into water. Table 2 below indicates whether each non-surfactantsolubilizing agent solubilized the solvents having an HLB value of a 5-7into the water at concentration of 15% of the base composition. TABLE 2Wt % of Non-Surfactant Solubilizing Agent 15%

Yes

Yes

Yes H₂N—CH₂—CH₂—OH Yes

Yes

Yes

[0086] A formulation useful as a hard surface cleaner was formed bycombining the components in the amounts listed in Table 3 below. TABLE 3Formulation A Component Weight % Water 31.8 Propylene Glycol PhenylEther¹ 20 Monoisopropanolamine 24 Tall Oil Fatty Acid 12 Linear alcoholethoxylate² 6 Na EDTA³ 6 Dye⁴ 0.2

[0087] Formulation A above provide a cleaning solution that can be usedas a dilutable degreaser for stainless steel surfaces, a non-dilutablealuminum pan cleaner that is metal safe, a hard surface cleaner, agraffiti remover or a floor cleaner and the like.

[0088] Aqueous solutions of ethylene glycol phenyl ether (EPh) of 100grams total were prepared and monoisopropanolamine (MIPA),2-amino-2-methyl-1-propanol (AMP), triethanolamine (TEA) andmonoethanolamine (MEA) was added at room temperature to each solutionuntil a single phase solution was observed. Results are reported inTable 4 below. TABLE 4 MIPA AMP TEA MBA % Eph in H₂O (Grams) (Grams)(Grams) (Grams) 1 3.5 4.8 4 2.3 2.5 16 12.3 14 12.7 5 26.8 21.5 28.926.9 10 32.2 26.8 42 40.5 15 33.5 28.7 47.8 45.4 20 32.9 29.2 47.9 44 3031.1 29 45.1 40 50 26 26.7 37.1 34 75 17.5 17.8 28.5 26.1

[0089] Tables 5-8 below illustrate this test data where the water,alcohol amine, and EPh are normalized to 100 weight % of the totalweight of water, alcohol amine and EPh in solution. TABLE 5 Water EphMIPA (wt %) (wt %) (wt %) 96 1 3 84 2 14 75 4 21 68 8 24 64 11 25 60 1525 53 23 24 40 40 20 21 64 15

[0090] TABLE 6 Water Eph AMP 95 (wt %) (wt %) (wt %) 94 1 5 87 2 11 78 418 71 8 21 66 12 22 62 15 23 54 23 23 39 39 22 21 64 15

[0091] TABLE 7 Water Eph TEA (wt %) (wt %) (wt %) 95 1 4 86 2 12 74 4 2263 7 30 58 10 32 54 14 32 48 21 31 36 36 28 19 58 32

[0092] TABLE 8 Water Eph MEA (wt %) (wt %) (wt %) 97 1 2 87 2 11 75 4 2164 7 29 58 10 32 56 14 30 50 21 29 37 37 26 20 60 20

[0093] Aqueous solutions of propylene glycol phenyl ether (PPh) orbenzyl alcohol were prepared and monoisopropanolamine (MIPA),2-amino-2-methyl-1-propanol (AMP), triethanolamine (TEA) andmonoethanolamine (MEA) was added at room temperature to each solutionuntil a single phase solution was observed. Normalized results based ontotal weight % are reported in Table 9 below. TABLE 9 Formulation wt % BC D E F Water 42 42 39 40 42 PPh 37 37 34 35 — Benzyl — — — — 37 AlcoholMIPA 21 — — — 21 AMP — 21 — — — TEA — — 27 — — MEA — — — 25 —

[0094] Those skilled in the art will recognize that the presentinvention may be manifested in a variety of forms other than thespecific embodiments described and contemplated herein. Accordingly,departures in form and detail may be made without departing from thescope and spirit of the present invention as described in the appendedclaims.

We claim:
 1. A composition comprising: a. a solvent at least partiallyimmiscible in water; b. water; and c. a solubilizing agent having aformula:

 wherein: R is (C₁-C₇)alkyl, substituted (C₁-C₇)alkyl, (C₁-C₇)alkoxy,substituted (C₁-C₇)alkoxy, (C₂-C₇)alkenyl, substituted (C₂-C₇)alkenyl,aryl, heteroaryl, cycloalkyl or heterocycly; R′ and R″ are independentlyselected from hydrogen, (C₁-C₇)alkyl, substituted (C₁-C₇)alkyl,(C₁-C₇)alkoxy, substituted (C₁-C₇)alkoxy, (C₂-C₇)alkenyl, or substituted(C₂-C₇)alkenyl;  wherein, when the solubilizing agent ismonoisopropanolamine the monoisopropanolamine is present in an amounteffective to form a stable single phase solution of solvent, water andmonoisopropanolamine.
 2. The composition of claim 1, wherein the solventhas a hydrophilic-lipophilic balance value of 5 to
 7. 3. The compositionof claim 1, wherein R is (C₂-C₄)alkyl.
 4. The composition of claim 1,wherein R′ and R″ is hydrogen.
 5. The composition of claim 1, whererinR′ and R″ is C₂ alkyl.
 6. The composition of claim 1, wherein thesolubilizing agent is monoisopropanolamine.
 7. The composition of claim1, wherein the solubilizing agent is 2-amino-2-methyl-1-propanol.
 8. Thecomposition of claim 1, wherein the solubilizing agent istriethanolamine.
 9. The composition of claim 1, wherein the solubilizingagent is monoethanolamine.
 10. The composition of claim 1, wherein thesolubilizing agent is 5-aminopentanol.
 11. The composition of claim 1,wherein the solvent is 1-phenoxy-2-propanol, 2-phenoxyethanol,(2-(2-butoxymethylethoxy)methylethoxy)-propanol,1-(2-butoxy-1-methylethoxy)-2-propanol, 1-butoxy-2-propanol, benzylalcohol or mixtures thereof.
 12. The composition of claim 1, whereinwhen the solubilizing agent is not monoisopropanolamine, the solvent ispresent at 1-99 wt %, water is present at 1-99 wt %, and solubilizingagent is present at 0.1-40 wt % of solvent, water and solubilizing agenttotal weight.
 13. The composition of claim 12, wherein the solvent ispresent at 5-50 wt %, water is present at 25-75 wt %, and solubilizingagent is present at 15-35 wt % of solvent, water and solubilizing agenttotal weight.
 14. The composition of claim 1, wherein solvent is presentat 5-50 wt %, water is present at 25-75 wt %, and solubilizing agent ispresent at 20-25 wt % of solvent, water and solubilizing agent totalweight.
 15. The composition of claim 1, further comprising a builder.16. The composition of claim 1, further comprising an enzyme.
 17. Thecomposition of claim 1, further comprising an enzyme stabilizing system.18. The composition of claim 1, further comprising an alkaline source.19. The composition of claim 1, further comprising a surfactant.
 20. Thecomposition of claim 1, further comprising an oxidizing source.
 21. Acomposition comprising: a. a solvent at least partially immiscible inwater; and b. a solubilizing agent having a formula: R₁—R—OH  wherein: Ris (C₁-C₇)alkyl, substituted (C₁-C₇)alkyl, (C₁-C₇)alkoxy, substituted(C₁-C₇)alkoxy, (C₂-C₇)alkenyl, substituted (C₂-C₇)alkenyl, aryl,heteroaryl, cycloalkyl or heterocycyl; R₁ is a nitrogen containingheterocycyl or a nitrogen containing hetroaryl.
 22. The composition ofclaim 21, wherein the solvent has a hydrophilic-lipophilic balance valueof 5 to
 7. 23. The composition of claim 21, further comprising water.24. The composition of claim 21, wherein R is (C₁-C₄) alkyl.
 25. Thecomposition of claim 21, wherein R₁ is heterocycyl.
 26. The compositionof claim 21, wherein the solubilizing agent is 1-piperidine ethanol. 27.The composition of claim 21, wherein the solvent is1-phenoxy-2-propanol, 2-phenoxyethanol,(2-(2-butoxymethylethoxy)methylethoxy)-propanol,1-(2-butoxy-1-methylethoxy)-2-propanol, 1-butoxy-2-propanol, benzylalcohol or mixtures thereof.
 28. The composition of claim 23, whereinthe solvent is present at 1-99 wt %, water is present at 1-99 wt %, andsolubilizing agent is present at 0.1-40 wt % of solvent, water andsolubilizing agent total weight.
 29. The composition of claim 23,wherein the solvent is present at 5-50 wt %, water is present at 25-75wt %, and solubilizing agent is present at 15-35 wt % of solvent, waterand solubilizing agent total weight.
 30. A method comprising: a.providing a solvent at least partially immiscible in water; and b.providing a solubilizing agent having a formula:

 wherein: R is (C₁-C₇)alkyl, substituted (C₁-C₇)alkyl, (C₁-C₇)alkoxy,substituted (C₁-C₇)alkoxy, (C₂-C₇)alkenyl, substituted (C₂-C₇)alkenyl,aryl, heteroaryl, cycloalkyl or heterocycly; R′ and R″ are independentlyselected from hydrogen, (C₁-C₇)alkyl, substituted (C₁-C₇)alkyl,(C₁-C₇)alkoxy, substituted (C₁-C₇)alkoxy, (C₂-C₇)alkenyl, or substituted(C₂-C₇)alkenyl; and c. combining the solvent and solubilizing agent withwater forming a stable single phase solution.
 31. The method of claim30, wherein the solvent has a hydrophilic-lipophilic balance value of 5to
 7. 32. The method of claim 30, wherein R is (C₂-C₄)alkyl.
 33. Themethod of claim 30, wherein R′ and R″ are hydrogen.
 34. The method ofclaim 30, wherein R′ and R″ hydrogen (C₂-C₄)alkyl.
 35. The method ofclaim 30, wherein the solubilizing agent is monoisopropanolamine. 36.The method of claim 30, wherein the solubilizing agent is2-amino-2-methyl-1-propanol.
 37. The method of claim 30, wherein thesolubilizing agent is triethanolamine.
 38. The method of claim 30,wherein the solubilizing agent is 5-aminopentanol.
 39. The method ofclaim 30, wherein the solvent is 1-phenoxy-2-propanol, 2-phenoxyethanol,(2-(2-butoxymethylethoxy)methylethoxy)-propanol,1-(2-butoxy-1-methylethoxy)-2-propanol, 1-butoxy-2-propanol, benzylalcohol or mixtures thereof.
 40. The method of claim 30, wherein thesolvent is present at 1-99 wt %, water is present at 1-99 wt %, andsolubilizing agent is present at 0.1-40 wt % of solvent, water andsolubilizing agent total weight in the stable single phase solution. 41.The method of claim 30, wherein the solvent is present at 5-50 wt %,water is present at 25-75 wt %, and solubilizing agent is present at15-35 wt % of solvent, water and solubilizing agent total weight in thestable single phase solution.
 42. A method comprising: a. providing asolvent at least partially immiscible in water; and b. providing asolubilizing agent having a formula: R₁—R—OH  wherein: R is(C₁-C₇)alkyl, substituted (C₁-C₇)alkyl, (C₁-C₇)alkoxy, substituted(C₁-C₇)alkoxy, (C₂-C₇)alkenyl, substituted (C₂-C₇)alkenyl, aryl,heteroaryl, cycloalkyl or heterocycyl; R₁ is a nitrogen containingheterocycyl or a nitrogen containing hetroaryl; c. combining the solventand solubilizing agent with water forming a stable single phasesolution.
 43. The method of claim 42, wherein the solvent has ahydrophilic-lipophilic balance value of 5 to
 7. 44. The method of claim42, wherein R is (C ₁-C₄)alkyl.
 45. The method of claim 42, wherein R₁is a heterocycyl.
 46. The method of claim 42, wherein the solubilizingagent is 1-piperidine ethanol.
 47. The method of claim 42, wherein thesolvent is 1-phenoxy-2-propanol, 2-phenoxyethanol,(2-(2-butoxymethylethoxy)methylethoxy)-propanol,1-(2-butoxy-1-methylethoxy)-2-propanol, 1-butoxy-2-propanol, benzylalcohol or mixtures thereof.
 48. The method of claim 42, wherein thesolvent is present at 1-99 wt %, water is present at 1-99 wt %, andsolubilizing agent is present at 0.1-40 wt % of solvent, water andsolubilizing agent total weight in the stable single phase solution. 49.The method of claim 42, wherein the solvent is present at 5-50 wt %,water is present at 25-75 wt %, and solubilizing agent is present at15-35 wt % of solvent, water and solubilizing agent total weight in thestable single phase solution.
 50. A product formed by the method ofclaim
 28. 51. A product formed by the method of claim 40.